DE2719720A1 - METHOD FOR PRODUCING BONDING - Google Patents

Description

The present invention relates to a new method for producing flexible bonds using One- or two-component polyurethane adhesives based on organic polyisocyanates and certain below polyhydroxy compounds explained in more detail.

The production of reactive adhesives based on organic polyhydroxy compounds and polyisocyanates are known (see e.g. GB-PS 1 408 510). The disadvantage of these adhesives is that to achieve high cohesive strengths and heat resistance Polyols and polyisocyanates with a high degree of branching must be used. These products result Adhesive films of low flexibility and are therefore used to bond flexible materials such as rubber or plastics, not suitable. The addition of plasticizers reduces the cohesive strength. Flexible adhesive films can be made from slightly branched polyols and polyisocyanates, but their cohesive strength is low.

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By adding customary inorganic or organic pigments, the required properties of flexible reactive adhesives could not be achieved satisfactorily up to now.

As has now been found, surprisingly, the production of flexible bonds has excellent cohesive strength according to the well-known principle of two-component polyurethane adhesives, which are an essential component of polyurethane contain fully reacting reaction mixture, then possible if as a reactant for the polyisocyanates instead of the classic polyhydroxy compounds used in polyurethane chemistry certain dispersions of polymers in organic hydroxyl compounds explained in more detail below be used. It has also been found that such dispersions of polymers can be used in Polyhydroxy compounds also enable the production of bonds based on the influence of moisture curing isocyanate prepolymers, which in turn are produced by reacting said dispersions with an excess are accessible to organic polyisocyanates.

The present invention thus relates to a process for the production of bonds of any substrates under Use of adhesives based on organic polyisocyanates and compounds with opposite isocyanate groups reactive hydrogen atoms, and optionally the customary auxiliaries and additives, the adhesives either being mixtures which react to form polyurethanes or contain, or where the adhesives contain moisture-curing, Reaction products containing free isocyanate groups from excess amounts of polyisocyanates and polyhydroxyl compounds represent or contain, characterized

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that dispersions are used as organic polyhydroxy compounds of polymers optionally containing isocyanate-reactive hydrogen atoms in organic Polyhydroxy compounds are used.

The polyhydroxyl component essential to the invention is a dispersion of polymers in organic polyhydroxyl compounds. The possibility opened up according to the invention the production of elastic bonds with high cohesive strength is primarily due to that in the dispersions essential to the invention both an elasticizing component and one made up of hard segments and thus component responsible for cohesion is included. As a rule, the polyhydroxyl compound represents here the elasticizing component and the dispersed polymer are those responsible for the cohesive strength Component with hard segments. However, also the reverse case in which the disperse phase for the elasticity of the bonds and the polyhydroxyl compound as a continuous phase for the cohesive strength Responsible for bonding is conceivable, but less preferred in practice.

In the case of the polyhydroxy compounds, which are essential to the invention Dispersions that form the continuous phase are generally those from polyurethane chemistry known polyhydroxy compounds having a molecular weight range of 2OO-4,000, preferably 400-2,5OO or around Mixtures of different polyhydroxy compounds with one average molecular weight of 2OO-4,000, preferably 4OO-2.5OO, with individual components of the mixtures also a Molecular weight between 62 and 200 or between 4,000 and 20,000.

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Suitable polyhydroxy compounds are, for example:

1. Simple polyhydric alcohols such as ethylene glycol,

1,2-propanediol, hexamethylene glycol, glycerine or trimethylolpropane;

2. Polyhydric alcohols containing ester groups, such as them in a manner known per se by reacting dicarboxylic acids such as adipic acid, phthalic acid, maleic acid, tetrahydrophthalic acid or hexahydrophthalic acid with excess amounts of alcohols such as, for example, the can be prepared under 1. mentioned above;

3. the polyether polyols known per se from polyurethane chemistry, as they are known per se by alkoxylation are accessible from suitable starter molecules. In addition to water, suitable starter molecules would be, for example the simple alcohols mentioned under 1. above; suitable alkoxylating agents would be ethylene oxide and / or Propylene oxide;

4. Natural oils containing hydroxyl groups such as in particular Castor oil.

In general, the polyhydroxyl compound is the elasticizing component. This means that as continuous phase either exclusively diols or diol mixtures or only too weakly branched Higher functional polyols or polyol mixtures which give rise to the problem are used. This means that triplets resp. Polyol mixtures with an average OH functionality of 3 or more than 3 an (average) molecular weight

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should have at least 600.

In addition to the polyhydroxy compounds mentioned above by way of example Of course, any other, for example acetal-amide or urethane groups can also be used as the continuous phase containing polyhydroxy compounds such as those in polyurethane chemistry are known per se, are used.

In the case of the polymers dispersed in the polyhydroxy compounds are polyaddition, polycondensation or polymerization products. The solids content of the essential to the invention Dispersion is generally between 3 and 60, preferably between 10 and 50 wt .-%, based on total dispersion.

The preferred polymers include polyisocyanate polyadducts, in particular, terminal hydroxyl groups built up from low molecular weight building blocks, primary or polyadducts containing secondary amino groups or semicarbazide groups. Under "low molecular weight" The building blocks here are in particular diisocyanates in the molecular weight range 112-300 and in the sense of the isocyanate polyaddition reaction at least difunctional compounds with isocyanate groups reactive To understand groups of the molecular weight range 32-30O.

Suitable diisocyanates for the preparation of the dispersed polyaddition products are e.g. ethylene diisocyanate, hexamethylene diisocyanate, 2,4-diisocyanatotoluene, 2,6-diisocyanatotoluene, 3,3, S-trimethyl-S-isocyanatomethyl-cyclohexyl isocyanate or 4,4'-diisocyanatodipheny! methane.

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Suitable low molecular weight structural components with groups that are reactive towards isocyanate groups are e.g. hydrazine, Ethylenediamine, hexamethylenediamine, 2,4-diaminotoluene, 2,6-diaminotoluene, 4,4'-diaminodiphenylmethane, aminoethanol, 2-amino-propanol, Ν, Ν-diethanolamine, ethylene glycol, trimethylene glycol, 1,2-propanediol, hexamethylene glycol, or also structural components containing ionic groups such as the sodium salt of 2- (aminoethyl) -2-aminoethanesulfonic acid. The diisocyanates and structural components mentioned by way of example with groups which are reactive toward isocyanate groups can in each case also be used as any mixtures that Concomitant use of in the sense of the isocyanate addition reaction monofunctional or polyfunctional structural components are of course also possible. In making the Polyaddition products are generally used in such amounts that the synthesis components are used for each Isocyanate group reactive group 0.9-1.1, preferably an isocyanate group, is available. The preparation of the dispersions of the polyadducts in the polyhydroxy compounds mentioned by way of example takes place generally in situ according to known prior art methods, such as those in DT-OS 2 513 815, DT-AS 1 260 142 or the German patent application P 25 50 797.5 are described.

In addition to such dispersions of polyadducts from low molecular weight synthesis components, such are used according to the invention, their polyadducts with the concomitant use of higher molecular weight synthesis components have been obtained, with "higher molecular weight" structural components, for example, polyhydroxypolyester or

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Polyhydroxypolyethers made from the structural components given above by way of example and a molecular weight of over 300 are to be understood. Dispersions of such polyadducts in the polyhydroxyl mentioned by way of example compounds can, for example, from the known aqueous polyurethane dispersions by mixing with the Polyhydroxy compounds and then distilling off the water according to German patent application P 25 50 860.5 can be obtained.

Dispersions suitable for the process according to the invention of polycondensation products in the polyhydroxy compounds mentioned by way of example are, in particular, aminoplast dispersions as they are accessible in a manner known per se, for example according to DT-OS 2 324 134.

In the case of the dispersions which can also be used according to the invention of polymers in the polyhydroxy compounds mentioned by way of example are primarily dispersions of natural or synthetic rubber in the hydroxy compounds mentioned by way of example, such as them from aqueous rubber latices according to the principle of German patent application P 25 50 860.5 by "dispersant exchange", i.e. addition of the polyhydroxy compound and removal of the water by distillation can be obtained.

Both the dispersions of isocyanate polyadducts which are particularly preferred in the context of the present invention from low molecular weight building blocks as well as the dispersions of Aminoplasts are typical examples in which

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the disperse phase that is preferably composed of hard segments and is therefore responsible for the cohesive strength Represent component, while the polyhydroxyl compound in these cases the elasticizing component represents. When using dispersions of elastomeric polymers, on the other hand, the disperse phase represents represents the elasticizing component, so that by suitable choice of the polyhydroxyl compound for the formation of hard segments care should be taken when performing the method according to the invention. This can be, for example achieved by using comparatively higher functional polyhydroxy compounds as the continuous phase will.

In the context of the present invention, polymer dispersions in polyhydroxyl compounds are particularly preferred whose disperse phase also has groups which are reactive toward isocyanate groups, namely the disperse phase Phase preferably have at least 0.1 equivalents of reactive Cr groups per 10Og solids and at the same time be at least difunctional in terms of the isocyanate addition reaction.

Another important aspect for the suitability of the polymer dispersions essential to the invention is the particle size of the dispersed particles, the associated sedimentation stability and the viscosity of the dispersions. In general, the particle size of the disperse phase should be between 0.01 and 10, preferably 0.01 to 1 to lie. The dispersants to be used according to the invention

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JO

In addition, ions are generally stable to sedimentation and have a viscosity of 20% at 25 ° C. of less than 100,000, preferably less than 10,000, particularly preferably less than 3,000 cP.

Particularly finely divided dispersions are obtained by the above-mentioned prior art processes, by the process of German patent application P 25 50 860.5 or by first preparing a solution of the polymer in a low molecular weight alcohol such as diethylene glycol, which solution is then prepared with a higher molecular weight polyol, preferably castor oil, is mixed, the dissolved polymer changing into a finely dispersed phase.

When carrying out the process according to the invention, the polymer dispersions are reacted with organic polyisocyanates, this reaction leading to polyurethanes either being allowed to proceed during the bonding process, ie the polyhydroxyl component and the polyisocyanate component being processed as a two-component system, or wherever in which a prepolymer containing free isocyanate groups is first prepared using an excess of polyisocyanate and this is then processed as an adhesive which cures under the influence of moisture. In the first-mentioned case, the amount of the reactants is generally such that for each isocyanate-reactive group present in the polymer dispersion, 0.8-1.5, preferably 0.95-1.30, isocyanate groups are present. In the preparation of the NCO prepolymers, there are 1.2 to 2.5, preferably 1.6 to 2.2, isocyanate groups for each isocyanate-reactive group

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for use. If an excess of isocyanate is used, however, it is not necessary to allow the reaction to form the NCO prepolymer to take place before the gluing process is carried out; rather, if an excess of NCO is used, the isocyanate addition reaction between the polyisocyanate component and the polyhydroxyl component during the gluing process is possible to carry out, the curing of the system during the gluing process is partially due to the reaction between isocyanate groups of the isocyanate component and isocyanate-reactive groups of the polyhydroxyl component and by reaction between isocyanate groups of the isocyanate component and humidity.

Aliphatic, cycloaliphatic, aromatic and heterocyclic polyisocyanates such as those described by W. Siefgen in Justus Liebigs Annalen der Chemie, 562, pages 75 to 136, are described, for example ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,12-dodecane diisocyanate, Cyclobutane-1,3-diisocyanate, cyclohexane-1,3- and -1,4-diisocyanate and any mixtures thereof Isomers, 1-isocyanato-3,3, S-trimethyl-S-isocyanatomethylcyclohexane (DAS 1 202 785), 2,4- and 2,6-hexahydrotolylene diisocyanate and any mixtures of these isomers, hexahydro-1,3- and / or 1,4-phenylene diisocyanate, perhydro-2,4'- and / or -4,4'-diphenylmethane diisocyanate, 1,3- and 1,4-phenylene diisocyanate, 2,4- and 2,6-tolylene diisocyanate and any mixtures of these isomers, diphenylmethane-2,4'- and / or -4,4'-diisocyanate, naphthylene-1,5-diisocyanate, Triphenyl methane 4,4 ', 4 "-triisocyanate, polyphenyl-

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polymethylene polyisocyanates, as obtained by aniline-formaldehyde condensation and subsequent phosgenation and described, for example, in British patents 874 430 and 848 671, perchlorinated aryl polyisocyanates, as described, for example, in German Auslegeschrift 1,157,601, containing carbodiimide groups Polyisocyanates as described in German patent specification 1,092,007, diisocyanates as described in American patent specification 3,492,330, polyisocyanates containing allophanate groups, for example in British patent specification 994 890, Belgian patent specification 761 and the published Dutch patent application 7 102 524 are described, polyisocyanates containing isocyanurate groups, as described, for example, in German patents 1 022 789, 1 222 067 and 1 027 394 and in German laid-open specifications 1 929 034 and 2 004 048, polyisocyanates containing urethane groups, such as those described, for example in the b Elgischen patent specification 752 261 or in the American patent specification 3,394,164, acylated urea group-containing polyisocyanates according to the German patent specification 1 230 778, biuret group-containing polyisocyanates, as for example in the German patent specification 1 101 394, in the British patent specification 889 050 and in French patent 7 017 514 describes polyisocyanates prepared by telomerization reactions, as described, for example, in Belgian patent 723 640, polyisocyanates containing ester groups, as described, for example, in British patents 956 474 and 1 072 956, in American patent 3,567 763 and are mentioned in German Patent 1 231 688, reaction products of the above-mentioned isocyanates with acetals according to German Patent 1 072 385.

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/ 3

As a rule, the technical ones are particularly preferred
Easily accessible polyisocyanates with aromatically bound isocyanate groups such as 2,4-diisocyanatotoluene and 2,6-diisocyanatotoluene consisting of these isomers
Mixtures, 2,4'-diisocyanatodiphenylmethane, 4,4'-diisocyanatodiphenylmethane, mixtures consisting of these isomers
or phosgenation products of aniline / formaldehyde condensates, such as those known as polyisocyanate mixtures of the diphenylmethane series, are used.

Mixing the dispersions essential to the invention with the polyisocyanate component is preferably carried out at room temperature, often using mechanical equipment served.

Even if equivalent amounts of the reactants are used, the mixtures represent a period of
0.2-3O, preferably 0.1 to 1 hour, represent liquids of a relatively low viscosity and can be applied to the materials to be bonded without difficulty using simple devices, for example a brush or a two-component metering system. After coating at least one of the surfaces to be bonded and joining the substrates to be bonded together, the adhesive reaches a after a short time
maximum adhesive strength. If desired, the reaction can also be carried out by using the catalysts known per se
be accelerated to accelerate the NCO / OH reaction.

Suitable catalysts are, for example, tertiary amines such as triethylenediamine, Ν, Ν'-diethylpiperazine or organic metal compounds, in particular tin compounds, such as, for example, dibutyltin dilaurate. The catalysts are optionally in

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Amounts of 0.01 to 5, preferably 0.1 to 3% by weight, based on the reaction components, are added.

When producing bonds, the adhesives are generally used at room temperature or at a slightly elevated temperature applied to the substrates to be bonded and then pressed. The application of higher temperatures is generally not required here. In this context, however, it should not go unmentioned that it is also possible is inventive, free isocyanate-containing adhesives either with the usual blocking agents for Isocyanate groups such as phenol or ^ -caprolactam in To convert derivatives with blocked isocyanate groups or the free isocyanate groups of the prepolymers with the aid of dimerization catalysts for isocyanate groups

to dimerize,

such as tert. Phosphines / whereby in both cases heat-activated adhesives are obtained, the isocyanate groups of which are only released by the action of heat. When processing such heat-activatable adhesives, processing temperatures of up to 180 C are then required. One area of application in particular for the last-mentioned heat-activatable adhesives with dimerized isocyanate groups would be, for example, tire cord bonding.

To modify the adhesives to be used according to the invention, natural or synthetic resins, anti-aging agents, pigments and fillers can be added to them. It is also possible to use water-adsorbing substances such as sodium aluminosilicate or solvents such as methyl ethyl ketone, but this is generally not necessary in the case of two-component adhesives.

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Any materials can be used with the method according to the invention such as paper, textiles, plastic, rubber, metal or ceramic materials are glued or jointed. That The method according to the invention is particularly suitable for gluing elastic materials, because of their inherent elasticity the cured adhesive does not adversely affect the elasticity of the composite material.

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Jib

Experimental part

"In-situ" production of diisocyanate polyaddition product dispersions from Table 1 according to the teaching of DOS 2 550 796 and DOS 2 550 797 in a polyol-water mixture

General working regulation

Apparatus: steel stirred kettle with reflux condenser and then descending condenser, storage vessel for the diisocyanate with inlet tube which is immersed in the liquid phase.

Carrying out the polyaddition reactions:

A mixture of the dispersants (polyols) and the chain extenders containing NH groups is poured into the stirred tank and water presented. The water content, based on the amount of dispersant, is between 15% by weight for a 20% dispersion and 40% by weight for a 50% dispersion. With a pressure of approx. 0.5 bar, nitrogen is used the liquid diisocyanate (mixture) in the at 70-85 ° C warmed mixture pressed in with vigorous stirring. The diisocyanate can be added rapidly, continuously or in portions take place that the exothermic polyaddition heats the reaction mixture to the boiling point of the water. After the addition of diisocyanate, which can optionally take place under "reflux", the temperature is the kettle contents are cooled to 50-75 ° C and almost immediately under reduced pressure with the distillation of the water started at 500-300 torr. After a vacuum of 40 Torr is reached, the internal temperature is gradually increased

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9O-11O ° C to remove the residual water. When the water content is less than 0.2 wt .-%, the still hot dispersion can be drained through a 0.1 mm pressure screen.

The generally spherical particles of the stable dispersions have a diameter of 0.1-2 .mu.m, mostly less than

1 to.

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CD OI O

Tabel

Characterization of the "in situ" prepared dispersions in dispersants containing ester and ether groups

Dispersion I. D i s ρ PHD e rse P h a ι s e J chain extension 6th Key figures + OH II Type I% PHD (OH) ₂ OH Conc. DI 3.9 HY NH [NH 8th 1 III 2 PHD (OH) ₂ 3 4th 5 T80 2.7 HY - IV PHD (OH) ₂ - 25th 21 .1 T80 6.7 HY + 2 90 V PHD (OH) ₂ 1 .70 20th 16.1 T80 5.4 HY + 2 91 VI PHD (OH) ₂ 1 .52 50 40.5 T80 2.2 HY + 2 .8 AA 91 VII PHD (OH) ₂ 1 .60 40 32.3 T80 4.4 HY + 4 .3AA 81 .5 VIII PHD (OH) ₂ 3.40 20th 15.4 T80 4.7 HY + 4 .4AA 81 .5 IX PHD (OH) ₂ 3.40 40 30.7 T80 1.4 HY + 4 .9AA 84.6 X PHD (OH) ₂ 2.78 40 31 .3 MDI 1.7 HY + 3 .OAA 69.6 XI PHD (OH) ₂ 4.81 25th 19.5 T80 3.4 HY + 7 .1 AA 73. 7 XII PHD (OH) 5.10 20th 14.6 T80 1.8 HY + 5 .7AA 73.7 XIII PHD (OH) ₄ 5.10 40 29.2 T80 1.8 HY + 5 .4 AA 69.6 XIV PHD (OH) ₄ 6.04 25th 17.8 T80 2.8 HY + 1 .4AA 69.6 6.04 25th 17.8 T80 4.5 HY + 6 .4AA 90 XV PHD (OH) ₂ 1 .70 20th 16.1 T80 0.9 HY + 3 .1 DAA 74.1 XVI APHS (OH) 5.00 40 29.3 .2DAA T100 .5AA 66.3 4.75 20th 14.0 T100 1.6MDA / DMS 66.0 5.31 20th 14.0 5.6 AAS + 3.8AA 7th 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100

IO CO CB

OO

Table 1 (continued)

oo ι

Dispersion .X. Manufacturing Dispersant 75 RIZ % 0H Disp. Viscosity cP / 25% II according to DOS 80 RIZ 1 III 10 50 PE 1 11 12th IV 2,550,796 60 PE 2 3.64 2600 V 11 80 RIZ 4.22 1400 VI " 60 RIZ 1 .61 3200 VII Il 60 PE 2 1 .66 1900 VIII Il 75 RIZ 4.56 13OO IX Il 80 RIZ 4.27 3200 X M. 60 PE 2 2.13 1200 XI Il 75 RIZ 4.84 7800 XII Il Γ37.5 RIZ
(_37.5 PE 1 4.90 1200 Il 80 RIZ 3.06 960 XIII Il 60 PE 2 5.15 1500 XIV It 80 RIZ 3.97 1340 XV 80 RIZ XVI M. 4.22 1900 Il 3.02 15OO 2,550,797 4.83 1000 Il 4.94 3400

ok

Explanations for the table

Column 1

Designation of the dispersions that serve as the starting component for the reactive adhesive.

Column 2

Typing of the disperse phase PHD polyhydrazodicarbonamide PHD (OH) polyhydrazodicarbonamide with χ

Hydroxyl groups in the molecule KPHD (OH) Cationic PHD with χ hydroxyl

groups in the molecule APHS (OH) Anionic polyurea with χ

Hydroxyl groups in the molecule

Column 3

Hydroxyl group content in% by weight, based on solids

Column 4

Conc. ^ Solids content in% by weight

Columns 5-7 starting components for the production of the disperse phase

Column 5

DI = diisocyanates in% by weight, based on

Solid

T8O 2,4- and 2,6-tolylene diisocyanate,

Mixture of isomers in the ratio 80:20 T100 pure 2,4-tolylene diisocyanate MDI 4,4'-diphenylmethane diisocyanate

Column 6

Chain extenders

HY hydrazine (is added as a monohydrate in a correspondingly larger amount)

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AA ethanolamine

DAA Ν, Ν-diethanolamine

MDA / DMS N-methyldiethanolamine, which is quarternized as diisocyanate polyadduct with 90 equivalent% of dimethyl

Columns 7 and 8 Key figures Column 7

Column 8

KZ _MH = NCO · 100 ^NH NH ~

KZ / = NCO NH / OH -

100

Column 9 Manufacturing methods according to DOS 2 550 796/7 in accordance with the general working instructions on p. 14

Column 10 Dispersants

RIZ = castor oil, OHZ 165

PE 1 = linear polypropylene glycol with secondary

OH groups (OH number = 56) PE 2 = linear started on 1,2-propanediol

Polyether made from propylene oxide and ethylene

oxide with approx. 6% primary OH groups,

OH number 56

Column 11 hydroxyl group content in% by weight, based on the total dispersion

Column 12

Viscosity of the dispersion at 25% in cP

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Tabel

Composition and properties of the reactive adhesives according to the dispersion process according to the invention (Table 1)

patent 1 Bez. I. V Type% ■ OH 70 ! 60 Conc. Disper-: Polyiso- ■ additive 0.3 K1 47.0V - t ! 43.5V - example 2 II VI 52 sion cyanate% disp. - 22.0V - 123Li 22.0 V I. 3 III VII 40 middle ! 0.3 K2 50.0V - 49.5 V! 10 PE 2 49.9 V i 4th 2 Il VIII 3 4th 78 5 6th 7; 8th - 51.0V 40.9V 51.0V 1 5 IV IX PHD 78 25th RIZ 37.5V 31.5V 6th Il X PHD (OH) - 1, 81 20th RIZ 47.0V 53 V 7th XI PHD (OH) ₂ 1 , 10 50 PE 1 16.6 V! 8th M. M. Il 10 Il Il Il 9 Il PHD (OH) ₂ 1, 04 40 PE 2 17.1V 10 XII " Il Il Il Il Il 11 PHD (OH) ₂ 3, It 20th RIZ 47.0V 12th XIII . PHD (OH) ₂ 2, 04 40 RIZ 13th XIV PHD (OH) ₂
, PHD (OH) ₂
j PHD (OH) ₂
: PHD (OH) ₂
PHD (OH) Ζ 2, 40 PE 2 14th XV It * 4, 70 25th RIZ 15th XVI Il 5, 00 20th RIZ 16 PHD (OH) ₂ 5, 75 40 PE 2 6, 31 25th RIZ 17th PHD (OH) ₂
PHD (OH) ₂ • I Il 18th KPHD (OH),
APHS (OH) ₂ It Il 19th 6, 25th TRIZ1 1
Ipezi 1 20th RIZ 1/ 20th PE 2 5, 40 RIZ 4, I 20 RIZ 5, 20th

Patent example

Table 2 (continued) Properties

1 pot Shear strength n. 9 days Heat resistance cm I. Remarks i j 22.7% 2 Time speed kp / cm 11: strength 50 ⁰ C 13th ! 3 immediately 76 min. ! 1 4th 9 10 85 i 12th 14th 5 39 ' 62 50 64 2 6th 31 ' 65 68; 75 1 7th ^ 24 h 15th 52 180 4th 8th 5 h 25th 71 180 2 9 > 24 h 24 105 180 10 3 h 31 96 180 2 11 31 ' 73 77 120 4th 12th 34 ' 61 115 ι 180 1 13th > 24 h 27 114 180 2 14th 39 ' 85 80 180 2 15th 30 ' 68 110 180 0 16 5 24 h 32 95 180 4th 17th 33 ' 88 132 180 5 18th > 18 h 62 53 180 19th 40 ' 71 84 180 20th 3.5 h 45 77 120 2 32 ' 58 70 95 > 24 h 22nd 82 180 33 ' 33 150 22 ' 45 160

Tabel

Comparative tests with the pure dispersants

1 2 3 4th 5 6th 7th 8th 9 10 11 12th 13th 14th A. - - - - RIZ 51 V - 38 ' 37 49 23 - B. - - - - PE 1 17.5V - -24 hours - - - - no
FiI
LJ 1 C. - - - - PE 2 17.5V - i24 h - - - - DIl
Il

is-

Explanations to the. Tables 2 and _ ^ 3

Column 1 Name of the patent examples according to the

i mdungsqsiTiäßen method

Columns 2-6 Characterization of the dispersions in glycols; compare table 1, columns 1-4 and 10

Column 7 polyisocyanates in wt. ~ I, based on those designated in column 2. Dispersers, which are inten: - :; · 'with the dispersion at room temperature

V = Po .: ypheny 1-po lyn · .::. '. Λ len-polyisccyanate n; t

an NCO salary v. of 30% by weight ("raw MDI")

^ ~ Tl is- ■; urethanisocysna ':) from 1 mol 1, 1, "■ Tr Lmethylolpiopc.:-. And 2, 4-Toluyiendiisocvünat as" S iiü. Ethyl acetate solution, NCG content + - 14.2% by weight

Column 8 Z-sentences in weight-i,;: -. absorbed the dispers ions before: column 2

K '= diazabicycioccrar.

K inndioctoat 2 = Z

PE 2 - Polyätherglykci see table 1, column

Column 9 pot life (times of applicability) ¹ = minutes
h = hours

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Tue ;. Check .. ': ■ :; J ^ r See: v.ent .Lu κ-ii t based on DIs :: 3 2b ': .. fir J. read Pri.ii.w; q v.irden not pretreated 3 jci \ er; hoir, - f ι viuekörper pocketed it glue?. Inside "5 L- ¹ .: Ύ;. '* .-: ■■ i- after the ' -.ι - ;: bstoi *: on crag there are 2 samples k .-: r; -. He se; - .. ::. iß-nffnueie - .. ;;., -; - ■■ '.-?;. nc-, overlapped area of 2 c ·: ""'"before ■ ■ .'- '! τ, jnd 2- ^: ;. π ::. ·. a pressure of 30 kp / cm aeprcH. ■:;:. :: ■ ■■: i ^ r.it ti ■;: .'_, de: .'-; cho rfl ^ tigkeit occurs in a Z ¹ ,: 1- ¹ ^: "- li- ; as <: hin _t ;;; i t t: a screw feed rate of 110 mm / min. The =: · -, t: Li., N v, j.rd ϊ ^.: - π _J r-iJ: .. ·: ·?:. 'I days after the pressing

. ^: C at we ii ¹ r-

: -'i ¹ '.' · -; t l--ki.lt occurs on a compound

: · .- ■ · ".er-'io , ^ and a 0.25 mm thick e:, y: ke {Best-cl 1-Nr , 387913) with a fcl · - ; ■■ ■,: ■ - ;; s%, Both test materials

-ίΐύ - :: Γι "ν .; - · ... * .: ■ ;;: - off ei: iCv _: - r -.:■ .: hev. ur.ö after an" open time "

1. -: ■; .. \, -li ^f ; -: · an overlapped area of tI ¹ L ^-1 IUi w.ii-'d then 1 min with 3, .. '. " Ι-ρ /' - ΐ 7:: cBr .. N. · ?. c: '; --- ^:;. L-igar iie it 9 days the composite is ^υ; ..: H nneravurcn / ■ :. η 5TV;. a constant force of 1, -250 ^kn: \ bi. .-i 'ίε Brer..e of 5 cnn exposed. The separation angle is .8 ::;'":. The table above shows the times that the bond can withstand the load. The test was terminated after 180 minutes and the separation distance was given in cm .

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20% PHD (OH) ₂ / SAN dispersion XVII solids ratio: 1: 1

Dispersant: castor oil; OH number 165 OH number / solids = 3.02% by weight; Viscosity at 25 ° C

1900 cP particle size: 0.5-3 µm

The dispersion is prepared in accordance with DOS 2,627,073 and the general working instruction, but stir instead of pure water, an aqueous styrene-acrylonitrile dispersion is used (Weight ratio of styrene acrylonitrile (= 72:28) into the mixture of the template, otherwise the same as the example XI, Table 1, worked.

Patent Example 21

100 parts by weight. Dispersion XVII and

47.1 parts by weight. Polyisocyanate V are used intensively at room temperature stirred and applied as a reactive adhesive. The pot life is 47 minutes,

immediately after 9 days shear strength kp / cm ² 51 72

Heat resistance at 50 C for 95 minutes

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25% PHD (OH) ₂ / ABS dispersion XVIII solids ratio 1: 1

Hydroxyl group content 3.02% by weight, based on solids Dispersant: castor oil; OH number 165 Viscosity at 25 ° C; 3200 cP particle size 0.1-1 .mu.m

The dispersion is prepared analogously to dispersion XVII, except that an aqueous dispersion is used instead of an SAN dispersion ABS (co-graft polymer) dispersion made from 70% by weight styrene-acrylonitrile copolymer and 30 wt .-% graft copolymer of polybutadiene, styrene and acrylonitrile) used.

Patent Example 22

The reactive adhesive mixture prepared analogously to Patent Example 21 with polyisocyanate V has a pot life of 40 minutes.

immediately after 9 days

Shear strength kp / cm ² 84 105

Heat resistance at 50 ° C for 155 minutes

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25% ABS dispersion XIX

Dispersing agent: castor oil, OH number 165 viscosity at 25 ° C 2300 cP Particle size 0.2 - 1 um

The dispersion is made by substituting the water from a 33% aqueous ABS dispersion by the appropriate amount Castor oil is carried out in such a way that the organic phase is initially charged and heated to 50.degree. The aqueous ABS dispersion is slowly added with stirring and at the same time the water is continuously distilled off under reduced pressure.

Patent Example 23

The 100 wt. Tin. Dispersion XIX and 37.5 wt. Tin. Polyisocyanate V produced reaction adhesive mixture has a pot life of 3 3 minutes.

immediately after 9 days

Shear strength kp / cm ² 78 95

Heat resistance at 50 ^° C. for 120 minutes

Comparative example D to patent examples 22 and 23

If, instead of the dispersion XIX, a polymer powder obtained in the usual way from the same aqueous ABS polymer is used, suspends this 25% in castor oil and mixes the suspension with the same amount of polyisocyanate V, in this way a mixture is obtained which is just as unsuitable as a reactive adhesive as is pure castor oil (see Comparative Example A, Table 3).

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2719 ^ 2 O 30

25% PHD (OH) ₂ / PMHS dispersion XX

Solids ratio 1: 1 dispersant: castor oil OH number / solids = 3, O2% by weight Viscosity at 25 ° C 2350 cP Particle size 0.2-2 .um

The dispersion is prepared analogously to Example 6 of DOS 2,639,254 by means of simultaneous in-situ production in castor oil Polyaddition and polycondensation reactions. The starting components for the polyadduct are those in Table 1, dispersion IX, components mentioned used for the polymethylene urea (PMHS) urea polycondensate and formaldehyde in a molar ratio of 1: 1.

Patent Example 24

The 100 wt. Tin. Dispersion XX and 37.5 wt. Tin. Polyisocyanate The mixture produced has a pot life of 34 minutes.

immediately after 9 days

Shear strength kp / cm 42

Heat resistance at 50 ° C for 23 minutes

25% PMHS (CH ₀ -OH) .. - Dispersion XXI ^ - χ

Dispersing agent: Castor oil Viscosity at 25 ° C 2800 cP Particle size 0.5 - 3.um

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The poly condensate dispersion containing methylol end groups is prepared according to the teaching of DOS 2 324 from urea and formaldehyde in a molar ratio of 19:20.

Patent Example 25

The 100 wt. Tin. Dispersion XXI and 41 wt. Tin. The mixture obtained from poly isocyanate V has a pot life of 21 minutes.

immediately after 9 days

2 shear strength kp / cm 61 80

Heat resistance at 50 C 125 minutes Patent example 26

100 wt. Tie. a mixture of equal parts of the 25% strength dispersions XI and XXI and 47 wt. TIn. Polyisocyanate V have a pot life of 26 minutes.

Immediately after 9 days heat resistance at 50 ° C 180 minutes / 2 cm

Shear strength kp / cm 78 102

6% PHD (OH) ₂ dispersion XXII Dispersant mixture: diethylene glycol / castor oil im

Weight ratio 9:85

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OH number / solids 5.74% by weight viscosity at 25 ° C Particle size 0.05-1 .mu.m

a) Preparation of a 40% PHD (OH) ,, solution in diethylene glycol according to DOS 2 638

from 23.5 wt. tin. 2,4-tolylene diisocyanate, 2.2 tin by weight. Hydrazine (used as monohydrate) and 14.3 wt. Tin. Diethylene glycol in excess Diethylene glycol.

The anhydrous solution has a viscosity of 3100 cP at 25 ° C.

b) Dispersion of solution a in castor oil

85 parts by weight. Castor oil are placed in a stirring apparatus and heated to 60.degree. Then slowly stir 15 parts by weight. warmed to 70 ⁰ C Diäthylenglykollösung intensively cool a can and the translucent dispersion to room temperature.

Patent Example 27

100 wt. Tie. of dispersion XXII and 7 5 wt. Tie. Polyisocyanate are mixed intensively. The pot life is 20 minutes.

immediately after 9 days

2 shear strength kp / cm 69

Heat resistance at 50 ° C 180 minutes / 4 cm

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271S720 33

% PHD (OH) ₂ -Suspension XXIII

Dispersing agent: polyalkylene oxide, PE 2 (Table 1) ^{0H "number} solid ^{5 '10 wt -%} viscosity at 25 ° C 970 cP particle size of 1 - 5 to

a) Production of a PHD (OH) ₂ powder

In analogy to dispersion X (Table 1), however, the same reaction components and amounts are used exclusively the polyaddition reaction carried out in water. When the diisocyanate is completely consumed the polyadduct can be isolated on a suction filter and, after thorough washing, on a tray in the drying cabinet dry at 80-120 ° C under vacuum. In a ball mill, a powder is produced within 24 hours obtained which has an irregular particle shape with a diameter of 2-6 µm.

b) suspension of the powder

60 parts by weight. PE 2 and 40 parts by weight. of the described under a Powders are thoroughly mixed until the suspension is free of agglomerates. Possibly a 60-70% masterbatch obtained on a three-roller mill can be diluted to 40% solids will.

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Patent Example 28

Analogously to patent example 12, a mixture is prepared with excess polyisocyanate V which has a pot life of has more than 24 hours.

immediately after 9 days

Shear strength kp / cm 42 71

Heat resistance at 50 ° C for 75 minutes

No film formation takes place without PHD (OH) ₂ ~ powder (comparative experiment C, table 3)

Patent Example 29

Preparation of a storage-stable NCO prepolymer dispersion 100 wt. the 40% PHD (OH) dispersion in PE 2 (see Example X, Table 1) and 6 parts by weight. N-methyldiethanolamine are heated to 80 ° C. in a stirred apparatus and 40.24 parts by weight. Diphenylmethane-4,4'-diisocyanate heated to 50 ^{° C. is added.} The theoretical free isocyanate content of 3.9% by weight is reached within 3-5 hours at a reaction temperature of 95-105 ° C.

The viscosity at 80 ^° C. is 27,500 cP. If moisture is excluded, the product is stable on storage at room temperature.

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AT

Adhesive properties In the open air, the pot life is approx. 3 hours

immediately after 9 days a) b) a) b) Shear strength kp / cm ² 28 54 64 87

Heat resistance at 50 ° C / minutes 180 180 a = without addition; b = with 2% by weight 1,4-butanediol

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Claims (2)

Claims 1. Process for the production of bondings of any Substrates using adhesives based on organic polyisocyanates and compounds with hydrogen atoms which are reactive towards isocyanate groups, and optionally the usual auxiliary and additives, the adhesives either being mixtures of the polyisocyanates which react to form polyurethanes and represent or contain polyhydroxy compounds, or where the adhesives contain moisture-curing, Reaction products containing free isocyanate groups from excess amounts of polyisocyanates and represent or contain polyhydroxy compounds, characterized in that the organic polyhydroxy compounds Dispersions of hydrogen atoms which may be reactive toward isocyanate groups containing polymers in organic polyhydroxy compounds. 2. The method according to claim 1, characterized in that as in the organic polyhydroxy compounds dispersed polymers isocyanate polyadducts used. Le A 18 041 - 35 - 809845/0288 ORIGINAL INSPECTED